Chemical depolymerization

Mucolytics reduce the viscosity of tenacious and purulent mucus, thus faciUtating removal. The distinction between mucolytics and other classes of expectorants is frequently blurred. Steam, sometimes in conjunction with surfactants or volatile oils, has long been used to decrease viscosity by physical hydration. However, agents that chemically depolymerize certain components of mucus are available. Trypsin and other proteolytic enzymes have shown good clinical activity because of their abiUty to cleave glycoproteins. Pancreatic domase, which depolymerizes DNA found in purulent mucus, also has shown clinical utihty. 

High-resolution 13C NMR studies have been conducted on intact cuticles from limes, suberized cell walls from potatoes, and insoluble residues that remain after chemical depolymerization treatments of these materials. Identification and quantitation of the major functional moieties in cutin and suberin have been accomplished with cross-polarization magic-angle spinning as well as direct polarization methods. Evidence for polyester crosslinks and details of the interactions among polyester, wax, and cell-wall components have come from a variety of spin-relaxation measurements. Structural models for these protective plant biopolymers have been evaluated in light of the NMR results. 

Isolation of the Biopolyesters. Cutin was obtained from the skin of limes using published methods (8,9). The final solvent extractions were omitted in studies of cutin-wax interactions. Typically, 20 limes provided 800 mg of powdered polymer. Suberized cell walls were isolated from wound-healing potatoes after seven days of growth (10), with a yield of 4.5 g from 22 kg of potatoes. Chemical depolymerization of both polyesters was accomplished via transesterification with BF3/CH3OH (11). 

Preliminary structural studies of cutin and suberin breakdown involved examination of 13C NMR spectra for insoluble residues that were resistant to chemical depolymerization. In cutin samples, flexible CH2 moieties in particular were removed by such treatments, but CHOCOR crosslinks and polysaccharide impurities were retained preferentially. A concomitant narrowing of NMR spectral lines suggested that the treatments produced more homogeneous polyester structures in both cases. Our current studies of cu-ticular breakdown also employ selective depolymerization strategies with appropriate enzymes (1,28). 

Low-molecular-weight fragments produced by chemical depolymerization and extraction of standard heparin consist of heterogeneous polysaccharide chains of molecular weight 2,000 to 9,000. The LMWH molecules contain the pentasaccharide sequence necessary for binding to antithrombin III but not the 18-saccharide sequence needed for binding to thrombin. Compared to standard heparin, LMWH has a 2- to 4-fold greater antifactor Xa activity than antithrombin activity. 

II) complexes. This method was also successfully applied to chemically derivatized GAGs that cannot be depolymerized by enzymes [62]. Similarly, capillary electrophoresis (CE) can be used for digested GAGs that are then detected by ultraviolet spectroscopy or mass spectrometry. Complexation of GAGs using copper (II) ions improved the sensitivity. However, complete separation of intact GAGs was not feasible by CE and most methods still rely on enzymatic or chemical depolymerization prior to analysis [46]. 

Examples of Extended Saccharide Domains Recovered EoUowing Enzymatic or Chemical Depolymerization of HS... 

Chemical depolymerization by reaction with certain agents to yield the starting monomers. 

The major disadvantage of chemical depolymerization is that it is almost completely restricted to the recycling of condensation polymers, and is of no use for the decomposition of most addition polymers, which are the main components of the plastic waste stream. Condensation polymers are obtained by the random reaction of two molecules, which may be monomers, oligomers or higher molecular weight intermediates, which proceeds with the liberation of a small molecule as the chain bonds are formed. Chemical depolymerization takes place by promoting the reverse reaction of the polymer formation, usually through the reaction of those small molecules with the polymeric chains. Several resins widely used on a commercial scale are based on condensation polymers, such as polyesters, polyamides, polyacetals, polycarbonates, etc. However, these polymers account for less than 15% of the total plastic wastes (see Chapter 1). 

Depending on the chemical agent used to break down the polymer, different depolymerization routes can be envisaged glycolysis, methanolysis, hydrolysis, ammonolysis, etc. In the following sections of this chapter, these alternatives are reviewed for those condensation polymers having the most significant commercial applications. It must be pointed out that a majority of the studies on chemical depolymerization of plastic wastes is reported in patents works published in the scientific literature are relatively scarce. 

Chemical depolymerization of polyesters has been mainly applied to polyethylene terephthalate (PET), the most common polyester on the market. Chemo-lysis of PET by a variety of methods has been known for many years. In fact, the chemical depolymerization of PET can be considered the starting point of plastic chemical recycling. 

The effect of the type of glycol used in the chemical depolymerization of PET has been studied at 200 °C, comparing the results obtained with ethylene glycol,... 

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